Method of finishing textile fibers with phosphate antistatic agents



United States Patent v 2,945,714 METHOD OF FINISHING TEXTILE FIBERS WITH PHOSPHATE AGENTS Calvin 'J'. Waitkus, Decatur, Ala., assignor to American Viscose. Corporation, Philadelphia, Pa., a corporation of Delaware No Drawing Filed Apr. 4, 1956, Ser. No. 575,928

6 Claims. 01. 117-4395 This invention relates more specifically to the treatment V of shaped articles comprising hydrophobic or substantially hydrophobic fiber or film-forming materials although hydrophilic fibers and films may also advantageously receive such treatment. While, in general, shaped articles of hydrophobic or substantially hydrophobic materials, e.g. films, may be treated by means of this invention, the primary concern is the. modificationof. textile fibers, to render themm o're amenable to textile processing More specifically these modifying treatments deal with antistatic protection, lubrication, and softening of the. fibers.

Many types of natural and synthetic fibers are poor electrical conductors and; tend to acquire and retain electrical charges: in, processing. It is therefore necessary to modify'the electrical qualities of the fibers so that they will generate a minimum amount of electricity during combing, carding, spinning and like operations where fibers are rubbed in constant frictional contact. The presence of static electricity on the fibers creates a severe problem because-it not onlyresults' in sticking of the fibers to the machinery, but also causes the fibers torepel each other during spinning operations so that it is difiicult to spin a coherent compact yarn therefrom.

Another requisite of a fiber-finishing treatment is the softening of' the fibers so. that a pliable yarn may be pro-- duced which will facilitate weaving and knitting. In knitting it is. particularly important that the yarnbe soft and pliable in order that the yarnwilt readily conform to the contour of the needles and thus producea closely knit fabric free: from such difficulties as stitch distortion, pinholes, laddering and the like. Weaving. alsore quires a. soft and: pliable yarn where a wearing iiieflfect is desired as in the production of such fabrics as talfeta and ninon.

In the manipulation oftextile materials it is also desirable} to: haste sufiicient lubrication in operational procc llrcsi wherein the: lubrication: is-furni's'hed by a coating on the yarn. This is particularly the case, for example, with dry-spun or melt-spun fibers after their production and prior to being wound, or twisted and wound; lubrication must be provided at the cap-edge to avoid chafing the yarn. Moreover, the knitting properties of the yarn are greatly improved by lubrication. It is clearly a great advantage if'theagent which reduces; electrification and. softens.- the yarn canbe applied simultaneously with. the lubricant, and particularly, if the agent will act as an emulsifier of the lubricating oil so as to facilitate the removal. of'the oil in the. final stages ofyarn processing.

For example, in preparing celluloseacetate yarn for further textile operations, itis advantageous to use an anhydrous finish composition because ofthe low strength of acetate fibers when wet-with aqueous media, and also because it is desired. to avoid the expense of drying to remove moisture from. the yarn prior to coning, knitting, etc. For these reasons, and others, the compositions to be used in the finishing baths of this invention are employed; as textile modifyingagentsjma mineral oil carrier.

It:v isgthercfore: an object of: thisinvention to: prepare 2,945,774 Patented July 19, 1960 ice a compound which will serve as a textile antistatic agent and textile softener.

A further object is to, prepare a textile modifying agent in accordance with the foregoing object which is soluble in oil and will also act as an emulsifier of the solvent oil. Still another object of this invention is to prepare a finishing medium from the modifying agents having the previously mentioned properties.

. In accordance with the present invention the essential ingredients of oily-type compositions for treating textiles comprises products of the reaction obtained by reacting oleic acid and an aliphatic polyamine to obtain the amide, then cross-linkingthe resulting oleylamidoalkylamine by reacting it with carbamic acid or a 2-substituted carbamic acid. Compounds of thislatter class are substituted ureas, thio-ureas, guanidines and guanyl ureas. After the cross; linkingoperation is completed, the reaction mass is heated in the presence of phosphoric acid or an alkyl phosphoric acid to further modify the principal cross-linked component of the reaction mix by the addition of a phosphoric anion. Although a series of reactions, such as those just described, may be expected to yield'a product comprising a number of compounds, the principal and functionally most important component of the entire process which provides the beneficial properties of the textile finishing compositions of the present invention is believed to have the following general formula:

. onmeii ietrcnarail-(0H,)Fir-R.

In the formula,.R R R and R may represent independently of each other eitherhydrogen or a simple alkyl or hydroxyalkyl radical of less than five carbons. The groups indicated. by D and D represent oxygen, sulfur, or an iminogithe number of such groups being designated byg which may range. from O to 3. Depending upon the nature: of the aliphatic polyamine used in the condensation with the-fatty acids,,theletter A is usedito represent either an amino (NH) group, a simple alkyl or alkylol substituted amino of less than five carbons such as (NC- H (NC H OH), oxygen, or sulfur. The figures f, j, e,. l, m

' and. 1 represent small whole numbers, 7 and may vary from 1 to 6, e and [from Oto 6, and m and t from 1 to 6, and any of the hydrogens in the CH groups may be substituted by the alkyl or hydroxy group. X in the phosphate anion representshydrogen or a simple alkyl group of from one to eight carbon atoms. The term oleoy as. used-herein refers to the oleic acid radical including the carbonyl group, but excluding the hydroxyl group. The term oleyl refers simply to the aliphatic carbon chain (C H5) and excludes the carbonyl and hydroxyl groups of oleic acid.

The condensation products used herein are readily prepared by heating equimolal quantities of oleic acid and the polyamine at temperatures from C. to 200 C. until the amidation reaction is: complete as shownby the loss of an equimolal quantity of water. The reaction mixture .is then cooled to about 180 C. and an additional one-half mole of urea or other carbamyl derivative is added as a cross-linking agent. Ammonia is rapidly liberated as the carbamyl-type radical becomes substituted during the cross-linking process. The temperature of the reaction mass is held between 170 C. and 200 C. and ammonia is liberated rapidly as, for example, the carbamyl group of urea cross-links with the nitrogen atoms of the oleylamide alkylene amino components most remote from the alkyl groups of said components. As the reaction mass cools to 80 C. to 140 C., phosphoric acid or an alkyl-phosphoric acid is added in quantities of 0.2 to 05 mole. To form the amide, oleic acid may be condensed with any of the short chain aliphatic polyamines, such as ethylene diamine, diethylene triamine, triethylene tetramine, tetra ethylene pentamine, hexanethylene diamine, hydroxyethylethylene diamine, ethylene diamine, 1,3-diamino isopropenyl, and beta-diamino diethyl ether.

The nomenclature of the condensate of oleic acid and polyamine may take such generally equivalent expressions (depending on the nature of the alkylene polyamine used as a reaction material) as oleoyl-alkylene diamine, N oleoyl-N48-hydroxyethylalkylene diamine, N acyl-N- w-hydroxalkylethylene diamine, fl-amino alkyl oleylamide, (w-hydroxyalkyl)-w-amino alkyl oleylamide, and fl-hydroxyethyl amino ethyl oleoylamide, or similar expressions for other condensates of oleic acid with an alkylene polyamine. A further expression generic to those just named is believed to be amino derivatives of oleylamides.

The compounds prepared in accordance with the I present invention are desired to be oil-soluble. Such solubility is obtained primarily through the presence of the oleoyl radical in the final reaction product. The use of certain polyamines favors the formation of the phosphatemodified compounds herein disclosed. For example, the presence of an alkyl or alkyl hydroxy group influences the initial condensing, the intermediate cross-linking, and final phosphate addition reactions by determining the nitrogen atoms provided by the polyamine at which the reactions take place. The terms polyamine, alkylene polyarnine, alkylene diamine, ethylene diamine, etc. as used to describe and claim the present invention are intended to include simple substituted groups attached to the alkylene polyamine nucleus, such as short chain alkyl, hydroxy or short chain hydroxyalkyl radicals.

The carbamyl compounds which are reacted with the oleoyl-polyamine condensate include urea, thioureas, guanidines, biurets, guanyl ureas and diguanidines. Another manner of designating these compounds is that they are amides of carbamic acid or Z-substituted carbamic acid. The latter term includes those compounds resulting from substitutions in carbamic acid resulting in such compounds as thiocarbamic and 2-amino carbamic acid. These compounds react with the oleyl amido alkylene condensate to produce cross-linking between imino nitrogen atoms of respective molecules of the condensate. It is believed that such cross-linking is substantially limited to the linking of molecules by pairs and further limited to the linking of but a single nitrogen atom of one molecule to a nitrogen atom of the mating molecule. The cross-linking is accomplished (ordinarily with the production of ammonia) by any divalent group derived from the above list of carbamyl-type compounds, such as the divalent carbamyl group which results when the amino groups of urea combine with a hydrogen atom from each of a pair of molecules of oleoylamido ethyleneamine. Other of such divalent cross-linking groups are ii t i The source of the phosphate ion which enters into the modification of a molecule of cross-linked fatty alkylene diamine may be phosphoric acid or an alkyl acid phosphate, such as methyl, ethyl, propyl, butyl, amyl or octyl phosphoric acid. The manner in which the phosphate ion is combined with the remainder of the molecule is believed to be a loose ionic association of an acid phosphate or alkyl phosphate radical with a free valence of the quaternized nitrogen atom in the ,6 position of one oleoyl-aliphatic polyamine group in a molecule of the cross-linked product.

In preparing the phosphoric acid-modified cross-linked condensate in the manner generally described above, chemical and physical evidence is such as to support the belief that in the final reaction step quaternization of the more basic nitrogen atom (in the ternary amide) adjacent the oleoyl radical takes place and the phosphate radical is attached to the nitrogen atom by an electovalency. The phosphoric acid-modified product is cationactive. It is likely that no one single compound results from its reaction and that other species of the initial condensation reaction are carried through the process to give diverse products. For example, when oleic acid and {3 hydroxyethylethylene diamine are condensed, the following species occur in decreasing order of probability:

(1) C 1H3sCONCzH4NH2 (predominate) (2) C 7H 3CONHCzH4NHCzH4OH (3) (31711330 0 0 CgH4NHCgH4NH: (least probable) Anhydrous solutions. of the phosphoric acid-modified urea cross-linked oleoyl-aliphatic polyamine products adapted for textile finishing are prepared preferably by dissolving said products in a refined white mineral oil. Such a mineral oil has a very low viscosity (Saybolt value of less than 70 at F., preferably not lower thanSO), no odor, no color, good emulsifiability, and favorable effect on the hand of the yarn. Preferably such an oil is parafiinic in type and refined from Pennsylvania crude. Compositions useful for finishing textiles, particularly cellulose acetate fibers, may be formulated from mineral oil and a phosphoric acid-modified, carbamyl derivative cross-linked, oleoyl-polyamine product dissolved therein within a range of from 5 to 25 percent concentration of the latter in the oil. However, the preferred range of concentration is in the approximate range of 10 to 20 percent. A concentration of 15 percent of the phosphoric acid-modified product in oil produces a textile'finish for acetate yarn which gives excellent all-around performance in respect to such factors as corrosion-resistance, softening of the fiber, elimination of static electricity, and emulsifiability for removal of the finish from the'yarn by aqueous media.

Exemplary embodiments of the invention are illustrated by the following examples:

Example 1 Ninety-six parts (2 moles) of a condensate of oleic acid and hydroxyethyl ethylene diamine, essentially a condensate, having the formula 0 CHsCHzOH C17H3s'C-N(C Hz) r-NH:

is further condensed with 32.7 parts (1 mole) of guanidine carbonate by slowly adding the carbonate to the reaction mixture with the temperature thereof maintained at C. The temperature is allowed to rise to C. The product obtained melted at 68 to 73 C. and was considered essentially a compound having the following probable formula:

0 CHzCHlOH C11Hza-CN C H: C H:N-H

(|J=NH Ci1Haa-CNCHzCHr-NH onloHion This product was reacted with 0.4 mole of methyl phosphoric acid at a temperature of 110 C. The principal co pensator the resulting. condensate. had the following probable formula:

4; no-i-oom d if 'biiHia CEN CIdzQEFN memoir NH C11H:'z-'-C'NCHCHr -n "the textile "fiaisa empo-swan was rpaaa item the above described methyl phosphoric acid-modified product by mixing 15 parts thereof with 85 parts of white mineral oil. The resulting solution was applied by a roll applicator to cellulose acetate yarn which was thereafter processed through con ing and. knitting machines. The yarn was tested for the presence of static charges at various points in the machinery and observed to carry no appreciable electrical charge. The yarn also exhibited good lubrication, at all points of contact with the machinery. This was particularly noticeable at the cap-edge of a cap twister. The yarn also had a good hand and the knitted fabric formed therefrom could be readily stripped of the finish composition by plain water.

This cross-linked product of the reaction described above was reacted with 0.5 mole of phosphoric acid at a temperature of 140 C. Of the product which resulted, the predominate component thereof is believed to have had the following probable formula:

Twelve parts of the product obtained in preparing the above phosphoric acid-modified, cross-linked, oleoyl-polyamine product was dissolved in 80 parts-of white mineral oil. The resulting solution was applied to continuous filament cellulose acetate yarn. The yarn was thereafter passed through the usual twisting and coning operations. No appreciable development of static elec- 6 trieity on-the yarn was observed as: a. result. of passing it through the machinery. The yarn thus processed had good ha'nd. Small test plates:- coated with the solution were exposed to the air and found over a period of a month not. to be subject to oxidative drying, or bacterial and fungi attack.

Example 3 I Several phosphate ion containi'ng' cross-linked 'oleoyl hydroxyethyl ethylene diamine condensates were separately prepared as follows: 2 moles of the condensate of 'olic acid and hydroiryethyl ethylene diamine were reacted with 1 mole 'of urea to obtain a product substan tially a compound having the following probable formula:

0 cfiiomofi C11HasG--NCHzCHr-N'H (i=0 C 7H a-C-NCHzCHrI TH o onzomorr Portions of this cross-linked reaction product were separately reacted with phosphoric acid, methyl phosphoric acid, ethyl phosphoric acid, propyl phosphoric acid, but'yl phosporic acid, amyl phosphoric acid, and octyl phosphoric acid. In each instance, the molecular structure of the principal component of the final product included the phosphate radical derived from the respective acid of the list just named in the manner illustrated bythe final structural formula "of Example 3. Separate finish compositions were prepared from each of the phos* phate ion-containing reaction products thus obtained by dissolving 15 'parts or each "of 'said final products in parts of white mineral oil (Textil'ine 50, Sonneborn Bros, Ii1c.). In all cases the resulting solutions were found to have good-to-excellent oil-solubility and emulsifiability. These solutions were also nonelectrostatic with respect to cellulose acetate fibers, and noncorrosive with respect to mild and stainless steels.

Although the final formula of each example is thought to describe the structure of the essential ingredient found in the reaction mass to which the phosphoric acid is added, it is well understood that chemically related products resulting from side reactions may accompany the formulation of a product in accordance with these formulae and may also contribute to the effectiveness of the compositions obtained at the completion by also reacting with a phosphoric acid from the group herein named.

Textile finishing baths containing the phosphoric acid modified condensates prepared in accordance with this invention are particularly adapted for the treatment of cellulose acetate continuous filament textiles. However, these products may be used in finishes designed for other textile fibers which are subject to the development of static electricity to an obnoxious degree. Such fibers may be formed, for example, from nylon, polyacrylonitrile, acrylonitrile polymers, and polyesters such as polyethylene terephthalate, sarans, and other vinyl copolymers. Suitable compositions for use in treating such fibers are those based on highly refined low-viscosity white mineral oils with 15 to 25 percent of the phosphoric acid-modified condensates dissolved therein.

Exhaustive tests conducted with cellulose acetate fiber treated with the oil base textile finishes prepared in accordance with the present invention were found to have the following advantages:

(1) The finish provides the proper degree of lubrication at the cap-edge which avoids chafed yarn and facilitates operational handling of the yarns.

.(2) The finish softens the yarn to an extent which promotes good performance in filling in weaving.

(3) It emulsifies the oil carrier so that the carrier may be easily removed for subsequent dyeing and finishing.

(4) It provides antistatic protection to the yarn suflicient to allow handling without further resort to antistatic devices.

It will not interfere with customary warp sizing practices.

While preferred embodiments of the invention have been shown and described, it is to beunderstood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Having thus described my invention, I claim:

-1. A method of finishing cellulose acetate textile fibers which comprises lubricating the same and inhibiting the accumulation of electrostatic charges thereon by applying to said cellulose acetate textile fibers a composition comprising a mineral oil and about 5 to 25% by weight of the reaction product of an acid from the group consisting of phosphoric acid and alkyl phosphoric acids wherein the alkyl radical contains 1 to 8 carbon atoms with a substituted carbamyl compound having the general formula wherein R is an alkyl group of 1 to 4 carbon atoms,

ROE l,

wherein ROH is an alkylol group of 1 to 4 carbon atoms, oxygen and sulfur, f and j vary from 1 to 6, e and l vary from 0 to 6, and m and tvary from 1 to 6, f, j, e, l, m and t all being whole numbers.

2. The method of claim 1 wherein e and l are zero.

3. The method of claim 1 wherein the reaction product of said phosphoric acid and said carbamyl compound are present in the mineral oil base composition in amounts between 10 and 20% by weight.

.4. The method of claim 2 wherein e, l and g are zero.

5. A method of claim 3 wherein said carbamyl compound is represented by the formula References Cited in the file of this patent I, UNITED STATES PATENTS 

1. A METHOD OF FINISHING CELLULOSE ACETATE TEXTILE FIBERS WHICH COMPRISES LUBRICATING THE SAME AND INHIBITING THE ACCUMULATION OF ELECTROSTATIC CHARGES THEREON BY APPLYING TO SAID CELLULOSE ACETATE TEXTILE FIBERS A COMPOSITION COMPRISING A MINERAL OIL AND ABOUT 5 TO 25% BY WEIGHT OF THE REACTION PRODUCT OF AN ACID FROM THE GROUP CONSISTING OF PHOSPHORIC ACID AND ALKYL PHOSPHORIC ACIDS WHEREIN THE ALKYL RADICAL CONTAINS 1 TO 8 CARBON ATOMS WITH A SUBSTITUTED CARBAMYL COMPOUND HAVING THE GENERAL FORMULA 